ZDHC Wastewater and Sludge Laboratory Sampling and Analysis Plan - Version 1.3 April 2021
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ZDHC Wastewater and
Sludge Laboratory
Sampling and
Analysis Plan
Version 1.3
April 2021
ZDHC Wastewater and Sludge Laboratory Sampling and Analysis Plan (SAP)
Version 1.3 | April 2021
1
Contents
1.0.0 Revision History 4 4.0.0 Sludge 24
2.0.0 Introduction 5 4.1.0 Sampling for Sludge 24
3.0.0 Wastewater 6 4.1.1 Sludge Sampling Points/Locations 24
3.1.0 Sampling for Wastewater 6 4.1.2 Sludge Sample Collection 25
3.1.1 Types of Samples and Sampling Points/Locations 6 4.1.3 Sludge Sample Containers and Preservatives 29
3.1.2 Wastewater Sample Collection 7 4.1.4 Sludge Sample Custody 32
3.1.3 Wastewater Sample Containers and Preservatives 8 4.1.5 Sludge Sample Shipments 32
3.1.4 Wastewater Sample Custody 12 4.2.0 Laboratory Analysis/Testing for Sludge 33
3.1.5 Wastewater Sample Shipments 12 4.2.1 Sludge Sample Receipt, Handling, and Custody 33
3.2.0 Laboratory Analysis/Testing for Wastewater 13 4.2.2 Sludge Sample Holding Time 34
3.2.1 Wastewater Sample Receipt, Handling, and Custody 13 4.2.3 ZDHC Sludge Parameters 36
3.2.2 Wastewater Sample Holding Time 14 4.2.4 Required Reporting Limits and Standard Test
3.2.3 ZDHC Wastewater Parameters 17 Methods for Sludge 36
3.2.4 Standard Test Methods for Wastewater 17 4.2.5 Quality Systems 37
3.2.5 Required Reporting Limits for Wastewater 18 4.2.6 Sludge Sample Storage 41
3.2.6 Quality Systems 18 4.3.0 Reporting and Deliverable Requirements 41
3.2.7 Wastewater Sample Storage 23 4.4.0 Data Validation 42
3.3.0 Reporting and Deliverable Requirements 23
3.4.0 Data Validation 24 Appendix A: Example Chain of Custody Form 43
Appendix B: Shipping and Customs Forms 44
Disclaimer:
Although the author and publisher have made every effort to ensure that the information in this publication was correct
at the time of publication, the author and publisher do not assume and hereby expressly disclaim any liability of any kind
to any party for any loss, damage, or disruption caused a) by errors or omissions, whether such errors or omissions result
from negligence, accident, or any other cause and/or b) from any use, decision made or action taken or any other kind of
reliance on the information contained in this publication by a reader or user of it.
ZDHC Wastewater and Sludge Laboratory Sampling and Analysis Plan (SAP) ZDHC Wastewater and Sludge Laboratory Sampling and Analysis Plan (SAP)
Version 1.3 | April 2021 Version 1.3 | April 2021
2 3
1.0.0 Revision History Version 1.3 1. Added sampling and analysis of conventional January
parameters specific to the ZDHC Leather Wastewater 2021
In the spirit of continuous improvement, the ZDHC Wastewater and Sludge Laboratory Guidelines Addendum. This includes: Faecal Coliform,
Sampling and Analysis Plan (SAP) will be reviewed on a regular basis and revised as needed Chloride, Sulfate and Total Dissolved Solids.
to incorporate learnings and opportunities identified during the practical application and 2. Added reference to and content from the ZDHC
implementation of these procedures. A historical record of updates to the SAP is noted in Wastewater and Sludge Sampling Procedure/Training.
the figure below. 3. Added guidance for composite wastewater sampling at
facilities that do not have continuous production cycles.
Figure 1: Revision History 4. Emphasised that the ZDHC specified methods for colour
Version Changes Time of and Chemical Oxygen Demand must be used. There are
Number Publication no exceptions.
5. Changed sample storage temperature from < 4°C to the
Version 1.0 Initial publication of the ZDHC Wastewater Laboratory June 2019 ISO recommended temperature of 2°C to 8°C.
Sampling and Analysis Plan. Version 1.3 Replaced Faecal Coliform with E.coli test. April 2021
Version 1.1 1. Added sampling and analysis procedures specific to August 2019
sludge.
2. Improved sampling and analysis procedures for 2.0.0 Introduction
wastewater.
• Ensured full alignment with ZDHC Wastewater The ZDHC Roadmap to Zero Programme takes a holistic approach to tackling the issue
Guidelines Version 1.1 requirements, including but of hazardous chemicals in the global textile, apparel, footwear and leather industry. This
not limited to standard method for analysis. holistic approach starts with the management of input chemistries, the management of
• Changed the expected sample temperature and day-to-day chemical use at production facilities (Suppliers), and the management of effluent
applied it to all relevant sections throughout the generated and discharged by Suppliers.
wastewater part of the document.
• Changed the recommended holding time for With regards to effluent management, the ZDHC Wastewater Guidelines (always refer
halogenated solvents – see Figure 3. to the latest version, publicly available on the ZDHC website) are in place to harmonise
• Adjusted the target value for Multi-Point Calibration wastewater parameters, limit values and test methods, as well as requirements for sampling,
in Figure 4. testing and reporting. This is an attempt to encourage and enable the industry, in particular
• Adjusted Calibration Check for Total Coliform in brands, suppliers (manufacturing facilities) and testing laboratories, to work towards the
Figure 5. same set of expectations.
• Updated and clarified the Reporting and
Deliverable Requirements in Section 3.3.0 to align This ZDHC Wastewater and Sludge Laboratory Sampling and Analysis Plan (SAP) document
with latest development within ZDHC. is one of the key elements to support implementation of the ZDHC Wastewater Guidelines.
Version 1.2 • Added sampling and analysis of parameters specific to April 2020 It does so by standardising procedures for laboratories to conduct sampling and analysis.
the ZDHC MMCF Wastewater interim guidelines. In this document the ZDHC Wastewater Guidelines encompass ZDHC Sludge, Textiles,
ZDHC Wastewater and Sludge Laboratory Sampling and Analysis Plan (SAP) ZDHC Wastewater and Sludge Laboratory Sampling and Analysis Plan (SAP)
Version 1.3 | April 2021 Version 1.3 | April 2021
4 5
3.1.2 Wastewater Sample Collection
Man-Made Cellulosic Fibres and Leather Wastewater Guidelines.
1. Samples shall be taken by ZDHC trained and accredited samplers only. Please refer to
Purpose the ZDHC Academy for training information.
This SAP provides a detailed framework for laboratories to perform testing to determine 2. Wastewater samples shall be collected as composite samples following ISO 5667 - 10
the concentration of parameters in wastewater and sludge. guidelines: “Water Quality Sampling Guidance for the preservation and handling of
water samples”.
The ZDHC Wastewater and Sludge Sampling Procedure/Training provides a detailed 3. Sampling using calibrated and refrigerated auto samplers is preferred. To ensure
framework for the sampling process. representative samples, composite sampling must be performed for no less than six
(6) hours, with no more than one (1) hour between discrete samples. Each discrete
Data Uses sample shall be of equal volume. The composite sample container must be cooled
Wastewater and sludge test data helps to promote the implementation of sustainable during sampling.
chemistry and best practices in the industry. 4. If necessary, laboratory personnel can collect discrete samples by hand for no less than
six (6) hours, with no more than one (1) hour between discrete samples. Each discrete
The laboratory must be aware of the importance of maintaining the integrity of test data sample shall be of equal volume and combined to produce one composite sample. The
generated under the ZDHC Programme. The test data may be used to make major decisions composite sample container must be cooled during sampling.
regarding manufacturing facilities. 5. All of the laboratory sample containers will be filled from the same bulk composite
sample. A minimum sample volume of 20-litres is needed to fill all the containers. The
laboratory may require extra volume for QA samples. The sampler shall coordinate
3.0.0 Wastewater extra volume requirements with the laboratory.
6. Samples must be taken during a time that represents continuous and normal production
3.1.0 Sampling for Wastewater and continuous and normal wastewater treatment. Collect wastewater samples in a way
that represents the entire production cycle. This may take a shorter or longer time than
3.1.1 Types of Samples and Sampling Points/Locations the specified 6-hour composite time.
7. Start the production cycle wastewater sampling after a time that compensates for the lag
Please refer to the ZDHC Wastewater Guidelines (WWG) for types of samples and sampling time in the effluent treatment system (ETP). For example, if the plant starts production
points/locations. The types of samples to be collected will depend on the testing option at 8:00 AM and the lag time in the ETP is 3 hours, then ETP wastewater discharge
decided upon by the brand and supplier (manufacturing facility), but limited to the two sampling will start at 11:00 AM.
testing options identified in the WWG. The WWG acknowledges the difference between 8. Samples must not be taken if the wastewater is diluted, for example, by heavy rainfall.
facilities with a direct discharge, indirect discharge and on-site zero liquid discharge 9. Wastewater flow data (volume/time) must be collected and reported with the laboratory
treatment plant. test results.
ZDHC Wastewater and Sludge Laboratory Sampling and Analysis Plan (SAP) ZDHC Wastewater and Sludge Laboratory Sampling and Analysis Plan (SAP)
Version 1.3 | April 2021 Version 1.3 | April 2021
6 73.1.3 Wastewater Sample Containers and Preservatives
Phenols P, G PTFE lined lid H2SO4 < pH 2
1. Figure 2 presents standard sample collection containers and preservatives for the 500-ml keep cool - between 2˚C and 8˚C
wastewater parameters specified in the ZDHC Wastewater Guidelines. Total Coliform P, G clean, sterile, 0.1 ml of 10% Sodium Thiosulfate
[bacteria/100ml] non-reactive, 125-ml keep cool - between 2˚C and 8˚C
2. The appropriate sample collection container and preservative can vary depending on P,G clean, sterile, 0.1 ml of 10% Sodium Thiosulfate
the standard test method used. Therefore, verify the proper container and preservative E.coli non-reactive, 125-ml keep in the dark and cool -
with the test method being used at the laboratory. between 2˚C and 8˚C
Persistent foam NA Measured in the field
Figure 2: Wastewater Sample Containers and Preservatives NaOH > pH12
Cyanide P, FP 1,000-ml 0.1 ml of 10% Sodium Thiosulfate
Wastewater Parameter Sample Container Standard Preservative keep cool - between 2˚C and 8˚C
Minimum Size (verify with lab method to be used) 4 drops 2N zinc acetate
Conventional Sulfide P, FP 100-ml NaOH > pH 9
Temperature NA Measured in the field keep cool - between 2˚C and 8˚C
Total Suspended Solids (TSS) P, G 200-ml keep cool - between 2˚C and 8˚C
Sulfite P, G, FP 100-ml 1-ml 2.5% EDTA
Total Dissolved Solids (TDS) P,G 200-ml keep cool - between 2˚C and 8˚C keep cool - between 2˚C and 8˚C
COD P, G, FP 100-ml H2SO4 < pH 2 Acute Aquatic Toxicity;
keep cool - between 2˚C and 8˚ C Luminus Bacteria
Total-N P, G, FP 100-ml H2SO4 < pH 2 Acute Aquatic Toxicity; Fish
keep cool - between 2˚C and 8˚C Egg G,FP 1,000-ml keep cool - between 2˚C and 8˚C
pH NA Measured in the Field Acute Aquatic Toxicity;
Colour [m-1] P, G, FP 500-ml keep cool - between 2˚C and 8˚C Daphne
(436nm; 525; 620nm) Acute Aquatic Toxicity;
BOD-5 day P, G, FP 1,000-ml keep cool - between 2˚C and 8˚C Algae
Ammonia-N P, G, FP 500-ml H2SO4 < pH 2 Glass, wide mouth FP HCl or H2SO4 < pH 2
keep cool - between 2˚C and 8˚C Total Hydrocarbon lined lid 1,000-ml keep cool - between 2˚C and 8˚C
Total-P P, G, FP 100-ml H2SO4 < pH 2
keep cool - between 2˚C and 8˚C Three x 40-ml amber HCl < pH 2
AOX P, G, FP 500-ml HNO3 pH 1-2, Carbon disulfide VOA vial no head- keep cool - between 2˚C and 8˚C
keep cool - between 2˚C and 8˚C space
Glass, wide mouth HCl or H2SO4 < pH 2 Chloride P,G,FP 100-ml keep cool - between 2˚C and 8˚C
Oil and Grease PTFE lined lid keep cool - between 2˚C and 8˚C
1,000-ml
ZDHC Wastewater and Sludge Laboratory Sampling and Analysis Plan (SAP) ZDHC Wastewater and Sludge Laboratory Sampling and Analysis Plan (SAP)
Version 1.3 | April 2021 Version 1.3 | April 2021
8 9Sulfate P,G,FP 100-ml keep cool - between 2˚C and 8˚C Perfluorinated and
P 1,000-ml
Polyfluorinated Chemicals no FP lined lid keep cool - between 2˚C and 8˚C
Shipping temperature calibrated room temperature water (PFCs)
indicator bottle thermometer Otho-Phthalates –
to +/- 1C˚ Including all ortho esters of G 1,000-ml FP lined lid keep cool - between 2˚C and 8˚C
Metals phthalic acid
Antimony, Chromium-total Polycyclic Aromatic keep cool - between 2˚C and 8˚C
G 1,000-ml FP lined lid
Cobalt, Copper, Nickel P, G, FP acid washed HNO3 < pH 2 Hydrocarbons
Silver, Zinc, Arsenic 250-ml keep cool - between 2˚C and 8˚C Volatile Organic Compounds Three x 40-ml amber HCl or H2SO4 or HNO3 < pH 2
Cadmium, Lead (VOC) VOA vial no keep cool - between 2˚C and 8˚C
G acid washed 40-ml 0.45µm filter in field, add buffer * headspace
Chromium-Hexavalent (VI) Brown Glass VOA vial to pH 9.0-9.5
keep cool - between 2˚C and 8˚C * Buffer = EPA Method 218.6. Dissolve 33g of ammonium sulphate in 75-ml of ASTM D1103 Type 1 or ISO 3696 water,
Mercury P, G, FP acid washed HNO3 < pH 2 add 6.5-ml of ammonium hydroxide. Dilute to 100-ml with ASTM D1103 Type-1 or ISO 3696 water.
500-ml keep cool - between 2˚C and 8˚C P= plastic, G= amber glass, FP= fluoropolymer
ZDHC MRSL V1.1
AP and APEOs: G 1,000-ml FP lined lid keep cool - between 2˚C and 8˚C
Including All Isomers 3. A temperature indicator bottle shall be included with each shipping container. The
Chlorobenzenes and G 1,000-ml FP lined lid keep cool - between 2˚C and 8˚C temperature indicator bottle will be clearly labelled.
Chlorotoluenes
Chlorophenols G 1,000-ml FP lined lid keep cool - between 2˚C and 8˚C 4. Field blanks shall be collected for the following parameters:
Dyes – Azo (Forming G 1,000-ml FP lined lid keep cool - between 2˚C and 8˚C a. Total-P
Restricted Amines) b. Coliform Bacteria
Dyes – Carcinogenic or G 1,000-ml FP lined lid keep cool - between 2˚C and 8˚C c. Mercury
equivalent Concern d. Halogenated Solvents
Dyes – Disperse (Sensitising) G 1,000-ml FP lined lid keep cool - between 2˚C and 8˚C e. Volatile Organic Compounds (VOC)
Flame Retardants G 1,000-ml FP lined lid keep cool - between 2˚C and 8˚C
Glycols G 1,000-ml FP lined lid keep cool - between 2˚C and 8˚C 5. The field blanks shall use the same containers as the samples and will be filled with
Three x 40-ml amber HCl < pH 2 ultra-pure laboratory grade water (ASTM D1193 or ISO 3696).
Halogenated Solvents VOA vial no head- keep cool - between 2˚C and 8˚C
space
Organotin Compounds G 1,000-ml acid keep cool - between 2˚C and 8˚C
washed FP lined lid
ZDHC Wastewater and Sludge Laboratory Sampling and Analysis Plan (SAP) ZDHC Wastewater and Sludge Laboratory Sampling and Analysis Plan (SAP)
Version 1.3 | April 2021 Version 1.3 | April 2021
10 113.1.4 Wastewater Sample Custody 3.2.0 Laboratory Analysis/Testing for Wastewater
Each sample shipment requires a Chain of Custody log that is maintained from the time 3.2.1 Wastewater Sample Receipt, Handling, and Custody
of collection, during the entire analytical process, and until sample disposal. A Chain
of Custody document provides a record of sample transfer from person to person. This 1. The laboratory shall be available to receive sample shipments at any time the delivery
document helps to protect the integrity of the sample by ensuring only authorised persons service is operating, including weekends.
have custody of the sample. An example Chain of Custody form is presented in Appendix
A. The sampling team must maintain physical custody, or use custody seal tape on the 2. The sample temperature shall be measured and recorded immediately upon opening
sample cool boxes the shipping container, and prior to unpacking the samples or removing the packing
material.
a. The laboratory shall use the shipping container temperature indicator bottle
3.1.5 Wastewater Sample Shipments reading as the sample temperature.
b. To determine the temperature, invert the bottle several times, remove the cap,
1. Use an a 24-hour (overnight) delivery service for samples that are shipped to a laboratory. and insert a calibrated thermometer.
c. Allow a minimum of three (3) minutes, but not greater than five (5) minutes
2. To avoid shipping delays and compromising sample holding times, contact the shipping prior to taking the measurement. The thermometer used shall be calibrated
company prior to sample collection. The shipping company can help determine the and capable of measuring within an accuracy of ±1°C.
appropriate customs arrangements that must be made. d. If a temperature indicator bottle is not present in the shipping container, an
alternative means of determining shipping container temperature can be
3. Appendix B provides sample shipping forms that may help to avoid delays in customs. used.
e. Under no circumstances shall a thermometer or any other device be inserted
4. Samples will be shipped in cool boxes with sufficient insulation and artificial refrigerant into a sample bottle for the purpose of determining shipping container
("blue ice"), or ice contained in double zip-lock bags, to maintain a sample temperature temperature. However, a small aliquot of the sample removed from the
of between 2°C and 8°C for the duration of transportation. Shipping containers that container can be used for measuring temperature. This small aliquot must be
leak fluid, such as melting ice water, will likely be returned to the shipper. discarded and not returned to the sample container.
f. Other devices, such as an infrared thermometer, which can measure
5. The sample cool boxes must be sealed with custody tape that is signed and dated by temperature may be used if they are calibrated to ±1°C.
the sampling crew. g. The desired sample temperature when it is received at the laboratory is
between 2°C and 8°C.
6. The sampler shall be responsible for all handling, processing, and custody of the i. If the sample temperature is greater than 8°C and less than
samples, including taking samples to the nearest servicing airport, bus station, or other 10°C, the laboratory shall note the issue and provide an exception
carrier. report with the sample test report.
ii. If the sample temperature exceeds 10°C when received at the
laboratory, the laboratory shall contact the client and inform them
of the temperature deviation. The client may decide not to perform
testing on these samples.
ZDHC Wastewater and Sludge Laboratory Sampling and Analysis Plan (SAP) ZDHC Wastewater and Sludge Laboratory Sampling and Analysis Plan (SAP)
Version 1.3 | April 2021 Version 1.3 | April 2021
12 133. The pH for all aqueous/water sample containers received by the laboratory shall be Figure 3: Wastewater Sample Holding Times
measured and recorded at the laboratory to demonstrate that proper preservation was
performed. Wastewater Parameter Recommended Holding Maximum Holding Time
a. Measure pH using test strips, an electronic hand-held pen, or pH meter. To Time
prevent sample contamination, measure the pH on a small aliquot of the Conventional
sample removed from the container. This small aliquot must be discarded Temperature measure in the field 15 minutes
and not returned to the sample container. Total Suspended Solids (TSS) 24 hours 7 days
b. Under no circumstances shall a strip or any device be inserted into a sample Total Dissolved Solids (TDS) 24-hours 7-days
bottle for the purpose of determining pH. COD 7 days 28 days
Total-N - 28 days
4. If the laboratory encounters problems with samples or related documentation (e.g. pH measure in the field 6 hours
mixed media, sample pH, sample documentation and paperwork such as Traffic Report/ Color [m-1] - 48 hours
Chain-of-Custody), the laboratory shall immediately contact the sampler for a resolution. (436nm; 525nm; 620nm)
BOD-5 day 6 hours 48 hours
Ammonia-N 7 days 28 days
3.2.2 Wastewater Sample Holding Time Total-P - 28 days
AOX - 6 months
1. In general, minimising the time between sample collection and analysis will provide Oil and Grease - 28 days
more reliable and representative analytical data. Phenols 24 hours 28 days
Total Coliform 6 hours 24 hours
2. Figure 3 presents both the recommended and maximum holding times for each of the [bacteria/100ml]
wastewater testing parameters. E.coli 6 hours 24 hours
Persistent foam measure in the field -
3. If a sample exceeds the maximum holding time the test results will be reported. Cyanide 24 hours 14 days
However, any test results that exceed the maximum holding time must be flagged with Sulfide - 7 days
the following data qualifier: “Maximum holding time exceeded. Red flag in the ZDHC Sulfite - 48 hours
Gateway - Wastewater Module. Probable error in results due to the holding time.” Aquatic Toxicity; Luminus
Bacteria, Fish egg, Daphne, 24 hours 48 hours
or Algae
Total Hydrocarbon - 28 days
Carbon disulfide 7 days 14 days
Chloride - 28 days
Sulfate - 28 days
ZDHC Wastewater and Sludge Laboratory Sampling and Analysis Plan (SAP) ZDHC Wastewater and Sludge Laboratory Sampling and Analysis Plan (SAP)
Version 1.3 | April 2021 Version 1.3 | April 2021
14 153.2.3 ZDHC Wastewater Parameters
Metals
Trace Metals 28 days 6 months The wastewater parameters, and the individual compounds for each parameter class, are
Chromium-Hexavalent (VI) 24 hours 28 days listed in the ZDHC Wastewater Guidelines.
Mercury - 28 days
ZDHC MRSL V1.1
Alkylphenol (AP) and
Alkylphenol Ethoxylates - 3.2.4 Standard Test Methods for Wastewater
(APEOs):
Including All Isomers 1. The ZDHC approved standard test methods are presented in the ZDHC Wastewater
Chlorobenzenes and - Guidelines, Appendix A Tables 1A-1B and Tables 2A-2N.
Chlorotoluenes Extraction:
Chlorophenols - 7-days from collection 2. The methods are based on requirements in the European Union, the United States of
Dyes – Azo - Analysis: America, India, and China. Alternate methods, such as those required by the regulatory
(Forming Restricted Amines) 40-days from extraction agency in the region where the wet processing/manufacturing occurs, may be used with
Dyes – Carcinogenic or - prior review from ZDHC, with the exceptions of colour and chemical oxygen demand
Equivalent Concern (COD).
Dyes – Disperse (Sensitising) -
Flame Retardants - 3. The specified ZDHC methods for colour and Chemical Oxygen Demand must be used,
Glycols - there are no exceptions. For more information refer to ZDHC Wastewater Guidelines.
Halogenated Solvents 7 days 14 days 4. Testing for persistent foam.
• Foam is a naturally occurring phenomena in aeration basins that enable biological
Organotin Compounds 24 hours wastewater treatment. To ensure accurate accounting of foam, sampling
Perfluorinated and personnel are expected to take a digital photo of the foam they witness within
Polyfluorinated Chemicals - Extraction: the wastewater treatment system. They should include photographs of the foam
(PFCs) 7-days from collection they witnessed in the final laboratory report, along with the time and date of
Otho-Phthalates – Including Analysis: taking such photos.
all ortho esters of phthalic - 40-days from extraction • The presence of foam is acceptable and meets the requirements of the
acid Guidelines if its colour is similar to the liquid in the aeration basin, dissipating,
Polycyclic Aromatic - no thicker than 45 centimetres by visual estimation, and is contained within the
Hydrocarbons (PAHs) aeration basin.
Volatile Organic Compounds 7 days 14 days • If the foam is higher than 45 centimetres by visual estimation or is not contained
(VOC) within the aeration basin, then it does not meet the requirements of the
Guidelines.
ZDHC Wastewater and Sludge Laboratory Sampling and Analysis Plan (SAP) ZDHC Wastewater and Sludge Laboratory Sampling and Analysis Plan (SAP)
Version 1.3 | April 2021 Version 1.3 | April 2021
16 173.2.5 Required Reporting Limits for Wastewater
Correction of
1. The minimum required reporting limits are presented in the ZDHC Wastewater For GC methods. injection
Guidelines. These were established with consideration to achieving these levels with Internal Substance with 50 – every error.
good laboratory practices. If the ZDHC reporting limits cannot be achieved, an alternate Standard physio-chemical 150% sample Method
method or a sub-contract laboratory must be used. properties similar specific:
to the analyte surrogate as
2. The Method Detection Limit (MDL) for each parameter must be determined first and alternative
is used to establish the reporting limit. The MDL will be established using ISO/TS
13530:2009 4.4.3. Choice of internal
Check standard or
3. The Reporting Limit (RL) will be established using ISO/TS 13530:2009 4.4.7. sample surrogate or a
preparation combination
4. Non-detected test results will be reported using the calculated RL for each parameter Substance which procedure thereof is method/
and not the ZDHC discharge limit. has similar and internal analyte dependent
Surrogate physio-chemical Method Every standard
properties to the specific sample correction.
analyte Method
3.2.6 Quality Systems specific:
internal
1. The minimum quality assurance measures for organic chemical analysis of wastewater standard as
and sludge are presented in Figure 4. alternative
Figure 4: Minimum Quality Assurance Measures for Organic Chemical Analysis
1 per
Measure Description Target Fre- Points to be checked Duplicate under- < 35 % batch
value quency
(examples)
Duplicate going complete RPD and Reproducibility of method
A. Routine process every 20
Method Covering sample 1 per Cleanliness of laboratory samples
blank preparation and < MDL batch glassware and equipment spike onto sample ± 20 % 1 per
measurement Matrix Spike matrix (duplicate) recov- batch Parameter recovery from sample
Calibration An independently 1 per Check instrument condition/drift, Matrix Spike undergoing ery and and matrix and reproducibility
Check sourced/prepared ± 20 % batch clean and re-calibrate, stability of Duplicate complete process < 35 % every 20
standard standards RPD samples
ZDHC Wastewater and Sludge Laboratory Sampling and Analysis Plan (SAP) ZDHC Wastewater and Sludge Laboratory Sampling and Analysis Plan (SAP)
Version 1.3 | April 2021 Version 1.3 | April 2021
18 19B. For method validation 2. The quality assurance testing in Figure 5 is required for each of the ZDHC wastewater
Multi-Point Min. 5-point r² ≥ Valida- parameters. This data may be requested and used by ZDHC to assess data quality and
Calibration calibration excl. 0.995 tion Linearity, working range validate the analytical results.
origin
Extract the Method Figure 5 – Required Quality Assurance Testing for Wastewater
Recovery standard through and Valida- Recovery without
Field Method Calibration Lab ISTD and
DQI
(LCS) the test procedure analyte tion influence of matrix Blank Blank Check* duplicate Surrogate
without matrix specific 1 per 1 per Every
Frequency 1 per Batch 1 in 20
Repeatability Matrix spike Method Robustness, recovery with matrix Batch Batch Sample
(matrix spike replicates under and Valida- influence, UoM, general fitness for Method
DQO < MDL < MDL +/- 20% +/- 35%
Specific
replicate) repeatability analyte tion use
conditions specific Conventional
less Temperature - - - - -
than Total Suspended Solids - - X X -
ISO/TS WWG MDL (TSS)
Limit of 13530:2009 RL Valida- Total Dissolved Solids - - X X -
Detection 4.4.3 Ideal: tion RL (TDS)
4.4.7 ≤½ COD - X X X -
WWG Total-N - X X X -
RL pH - - X - -
Colour [m-1] - X X - -
Note: (436nm; 525; 620nm)
• General suitability of the analytical approach is demonstrated via method validation. BOD-5 day - X X - -
• Matrix to be encountered for wastewater and sludge analysis is less diverse/concentrated than for process chemicals Ammonia-N - X X X -
(ZDHC MRSL). Total-P X X X X -
• Therefore, initial method validation is deemed to sufficiently cover most sample types and a comparatively leaner QC AOX - X X X -
programme is applied. Oil and Grease - X X X -
• Specific, problematic sample matrices, which are not covered by the validation, require additional QC measures. Phenols - X X X -
• In case of conflict, quality assurance measures specified by the applied standard, the accreditation body or local authority Total Coliform X X - X -
shall prevail. [bacteria/100ml]
E.coli X X - X -
Persistent foam - - - - -
Cyanide - X X X -
Sulfide - X X X -
Sulfite - X X X -
ZDHC Wastewater and Sludge Laboratory Sampling and Analysis Plan (SAP) ZDHC Wastewater and Sludge Laboratory Sampling and Analysis Plan (SAP)
Version 1.3 | April 2021 Version 1.3 | April 2021
20 21Aquatic Toxicity; 3.2.7 Wastewater Sample Storage
Reference
Luminus Bacteria, Fish - X X -
Toxicant
egg, Daphne, or Algae
1. All samples will be stored under custody at 2˚C - 8˚C (unless otherwise specified by the
Total Hydrocarbon - X X X -
standard test method).
Carbon disulfide X X X X X
Chloride - X X X -
2. The samples may be disposed of 60 days after the final laboratory report is issued.
Sulfate - X X X -
Metals
Metals - X X X X
3.3.0 Reporting and Deliverable Requirements
Chromium-Hexavalent
- X X X X
(VI)
Mercury X X X X X Reporting1 here means the submission of test data/results onto the ZDHC Gateway –
ZDHC MRSL V1.1 Wastewater Module by ZDHC Accepted Laboratories on behalf of suppliers. It is vital that
Alkylphenol (AP) and the integrity of the test data in the Gateway is at its highest possible standard. This will,
Alkylphenol Ethoxylates among other things, support the ZDHC Roadmap to Zero Programme in making scientific
- X X X X
(APEOs):
and data driven decisions necessary to shape the future of our industry.
Including All Isomers
Chlorobenzenes and
- X X X X 1. All test data must be reported using the ZDHC Gateway Electronic Data Reporting
Chlorotoluenes
Chlorophenols - X X X X (EDR) System. The EDR guidelines and reporting template are publicly available on the
Dyes – Azo (Forming ZDHC website.
- X X X X
Restricted Amines)
Dyes – Carcinogenic or 2. The use of reporting formats other than those approved in the EDR will be deemed
- X X X X
equivalent Concern
non-conformance. Such data is unacceptable and resubmission in the specified format
Dyes – Disperse
- X X X X will be required.
(Sensitising)
Flame Retardants - X X X X
Glycols - X X X X 3. All ZDHC Accepted Laboratories are expected to follow the data reporting requirements
Halogenated Solvents X X X X X specified in the ZDHC Gateway Electronic Data Reporting (EDR) System Guidelines for
Organotin Compounds - X X X X wastewater and sludge, available on the ZDHC website.
Perfluorinated and
Polyfluorinated X X X X X
Chemicals (PFCs)
Otho-Phthalates –
Including all ortho esters - X X X X
of phthalic acid
Polycyclic Aromatic - X X X X
Hydrocarbons (PAHs)
Volatile Organic
X X X X X
Compounds (VOC)
1
For more information please read the latest version of the ZDHC Wastewater Guidelines and the ZDHC Gateway User Terms
and Conditions document.
* calibration check conducted with a second source standard
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22 233.4.0 Data Validation
a. Any Liquid Sludge Waste (not to be confused with wastewater)
• ZDHC routinely requests laboratory QA/QC information from randomly selected ZDHC containing low or high amounts of solids.
Accepted Laboratories. The following information may be requested for data review: b. Anaerobically Digested Sludge
a. Calibration Curves c. Aerobically Digested Sludge
b. Method Blank Instrument Reports d. De-watered Sludge Cake
c. Instrument Calibration Check Reports e. Primary Sludge
d. Laboratory Control Sample Instrument Reports f. Tertiary Sludge
e. Laboratory Duplicate Instrument Reports g. Biomass Sludge (Secondary Sludge)
f. Matrix Spike and Matrix Spike Duplicate Instrument Reports h. Compost Product
g. Sample Custody Documentation i. Dried Sludge Solid Waste
j. Incinerator Ash
• The quality assurance and quality control results associated with the ZDHC sample will
be assessed by ZDHC to validate the analytical data. Quality assurance results that fail
to meet ZDHC guidelines may result in the rejection of sample results. 4.1.2 Sludge Sample Collection
1. Samples shall be taken by ZDHC trained and accredited samplers only. Please refer to
4.0.0 Sludge the ZDHC Academy for training information.
4.1.0 Sampling for Sludge 2. Samples must be taken during a time that represents continuous and normal production
and continuous and normal wastewater treatment. Collect sludge samples in a way that
4.1.1 Sludge Sampling Points/Locations represents the entire production cycle. This may take a shorter or longer time than the
specified 6-hour composite time.
1. Please refer to the ZDHC Wastewater Guidelines (WWG) for the definition of sludge and
the main purpose of testing sludge. Depending on the chosen testing option described 3. Start the production cycle sludge sampling after a time that compensates for the lag
in the WWG Section 9, sludge samples may be collected. time in the effluent treatment system (ETP). For example, if the plant starts production
at 8:00 AM and the lag time in the ETP is 3 hours, then ETP sludge sampling will start
2. The suppliers must identify, to qualified sampling personnel, the points where sludge at 11:00 AM.
is generated and stored at the Supplier. The qualified sampling personnel will make a
final determination as to the proper sampling locations. 4. Sludge samples shall be collected as composite samples following: USEPA 833-B-89-
100 “POTW Sludge Sampling and Analysis Guidance Document”. The ISO 5667- 13
3. Sludge samples will be collected to representative all of the sludges generated by the “Guidance on Sampling Sludge” document also provides reference sludge sampling
Supplier’s ETP (Effluent Treatment Plant) that are disposed of or reused. guidance and more detailed information on sampling devices.
4. It may be necessary to collect various types of sludge samples throughout a given 5. The most appropriate way of sampling in any situation depends on several factors:
Supplier’s ETP, including: a. safe access to the sampling point by personnel.
ZDHC Wastewater and Sludge Laboratory Sampling and Analysis Plan (SAP) ZDHC Wastewater and Sludge Laboratory Sampling and Analysis Plan (SAP)
Version 1.3 | April 2021 Version 1.3 | April 2021
24 25b. the practicality of installing and maintaining automatic equipment, if the entire sludge volume.
appropriate.
c. the practicalities of safely interrupting a stream of moving liquid sludge or 9. For collecting liquid sludge samples:
cake when manually sampling and the nature of the chamber or tank design a. It should be noted that thin liquid sludges (of lower solids content) require
with respect to stratification of liquid sludges. the preparation of relatively large volumes of the sampled material to provide
sufficient dry matter to facilitate a truly representative analysis of constituents,
6. In general, automatic sampling devices, which are widely used for wastewater streams, e.g. metals. The analyst should always be consulted as to the quantities of
do not work well for sludge streams because of the solids content and viscosity of sludge required, and the sample reduced accordingly in the field before
sludges2. Therefore, manual composite sampling may be required. returning to the laboratory4.
b. All of the laboratory sample containers will be filled from the same bulk
7. ISO 5667-13 describes multiple sample collection devices. composite sample. A minimum sample volume of six (6) litres is needed to fill
all the containers. The laboratory may require extra volume for QA samples.
8. For collecting solid sludge samples3: The sampler shall coordinate extra volume requirements with the laboratory.
a. When sampling heaps of air-dried sludge lifted from drying beds or stockpiles c. Collect samples in a manner that represents the entire flow at the sampling
of sludge cake, it is important to obtain portions of sludge from throughout point over the entire sampling period5.
the mass and not just from the surface layer. d. These procedures should be followed when sampling from a tap6:
b. For either de-watered cakes, dried sludge powder or compost product, • Allow sufficient time following pump start-up to clear the line of stagnant
combine equal amounts collected at various locations/depths for each grab sludge.
sample. This will obtain a more representative composite sample. • Allow sludge to flow from the tap for several seconds prior to sampling. This
c. To produce a sample from multiple sample locations (e.g. two or more de- will flush out stagnant sludge and solids accumulated in the tap.
watering units), combine the grab samples from each location (equal amounts e. Before drawing a sludge sample, rinse each piece of sampling equipment
or weighted, based on flow or solids flux data) in a plastic or stainless-steel three (3) times with sample to reduce the chance of contamination from the
bucket and thoroughly mix the sample (with a scoop or spoon). Then transfer previous grab.
it to sample containers. f. To prevent solids separation in the sample, use glass, PTFE-coated stirring
d. When sampling drying beds, divide each bed into quarters. From the center rods, or stainless-steel spoons to mix the sample before splitting or
of each quarter, collect a single core sample through the entire depth of the transferring any portion of it to another container.
sludge using a coring device. Usually, a small amount of sand will be collected; g. With sludge processing trains, samples from taps on the discharge side of
avoid large amounts of sand. Combine and thoroughly mix in a plastic or sludge pumps are well mixed since flow at this point in the system is turbulent
stainless-steel bucket and transfer to sample containers. with minimal solids separation within the flow stream.
e. A sample shall be collected as one composite sample of that sludge type. h. If a sample is drawn from a tap on a pipe containing sludge that is distant
The composite sample shall represent the entire volume of that sludge type. from the sludge pumps, the average flow velocity through the pipe should
A sampling grid pattern may be needed, and core samples may be required be greater than 2 feet per second (fps). Average velocities of less than 2 fps
to obtain a representative sample. Collect samples in a manner that represents result in solids separation and settling, and affect sample solids content,
5
USEPA 833-B-89-100: POTW Sludge Sampling and Analysis Guidance Document
2
USEPA 833-B-89-100: POTW Sludge Sampling and Analysis Guidance Document 6
USEPA 833-B-89-100: POTW Sludge Sampling and Analysis Guidance Document
3
ISO 5667- 13: Guidance on Sampling Sludge 4
ISO 5667- 13: Guidance on Sampling Sludge
ZDHC Wastewater and Sludge Laboratory Sampling and Analysis Plan (SAP) ZDHC Wastewater and Sludge Laboratory Sampling and Analysis Plan (SAP)
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26 274.1.3 Sludge Sample Containers and Preservatives
depending on the location of the tap (top, side or bottom of the pipe).
i. Given a choice, a tap on the side of the pipe is preferable. In addition, the 1. Figure 6 presents standard sample collection containers and preservatives for sludge
tap should be a large size to encourage draw from the entire cross-section of samples generated from a wastewater/effluent treatment plant.
flow when fully open.
j. If the sludge solids tend to separate into different fractions care must be 2. The appropriate sample collection container and preservative can vary depending on
given to mixing the samples adequately to obtain a representative sample. the analytical procedure used. Therefore, verify the proper container and preservative
If the fractions cannot be mixed, then separate samples are to be collected. with the analytical method being used at the laboratory.
This is because some pollutant parameters are predominantly associated
with the solid fraction while others are associated with the liquid phase. 3. Caution should be exercised since containers can become pressurised due to gas
production in wastewater sludges and explosive situations can occur. Care should be
10. Sampling equipment must be made of materials which will not contaminate or react taken, particularly when glass containers are used, to prevent a build-up of gas pressure
with the sludge. The best material choices are glass and stainless steel because they and to minimise the dispersion of fragments if an explosion occurs.8
are relatively inert.7
11. Sludge flux (weight/time) and/or flow data volume/time, if available, must be collected 4. A temperature indicator bottle shall be included with each shipping container to measure
and reported with the analytical results. the temperature of samples at their time of arrival at the laboratory. The temperature
indicator bottle will be clearly labelled.
12. The facility shall provide all necessary assistance to the sampler. Including but not
limited to: 5. When collecting samples, fill the container to 4/5 full to enable expansion of samples
• access to all relevant areas. and provide room for gases that may be produced.9
• provision of information e.g. flow rates, facility layout, flow path, processes.
• relocation of parts of solid sludge piles where needed to access deeper layers. 6. For solid sludge samples (cake, powder, ash), adding a chemical preservative is
• provision of safety gear and warnings on any specific hazards present. generally not useful since the preservative does not usually penetrate the sludge matrix.
Preservation consists of keeping the temperature between 2°C and 8°C.
8
ISO 5667- 13: Guidance on Sampling Sludge
7
USEPA 833-B-89-100: POTW Sludge Sampling and Analysis Guidance Document
9
USEPA 833-B-89-100: POTW Sludge Sampling and Analysis Guidance Document
ZDHC Wastewater and Sludge Laboratory Sampling and Analysis Plan (SAP) ZDHC Wastewater and Sludge Laboratory Sampling and Analysis Plan (SAP)
Version 1.3 | April 2021 Version 1.3 | April 2021
28 29Figure 6: Sludge Sample Containers and Preservatives Perfluorinated and G 1,000-ml NO PTFE lining 0.008% Na2S2O3 V/W
Polyfluorinated Chemicals wide mouth cool < 4˚C
Sample Container Standard Preservative (PFCs)
Sludge Parameter Minimum Size (verify with lab method to G 1,000-ml PTFE lining wide H2SO4, pH 12 pH, < 13 pH, Organotin Compounds G 1,000-ml acid washed keep cool between 2˚C and
Cyanide PTFE lined lid cool < 4˚C PTFE lining wide mouth 8˚C
approx 2-ml 10N NaOH Halogenated Solvents 1:1 HCl, HNO3, or H2SO4
Metals Volatile Organic Compounds Three x 40-ml VOA vial, no pH4.1.4 Sludge Sample Custody 4.2.0 Laboratory Analysis/Testing for Sludge
Each sample shipment requires a Chain of Custody log that is maintained from the time 4.2.1 Sludge Sample Receipt, Handling, and Custody
of collection, during the entire analytical process, and until sample disposal. A Chain
of Custody document provides a record of sample transfer from person to person. This 1. The laboratory shall be available to receive sample shipments at any time the delivery
document helps to protect the integrity of the sample by ensuring only authorised persons service is operating, including weekends.
have custody of the sample. An example Chain of Custody form is presented in Appendix
A. The sampling team must maintain physical custody, or use custody seal tape on the cool 2. The sample temperature shall be measured and recorded immediately upon opening
boxes, until the samples are handed off to the shipping company or laboratory. the shipping container, and prior to unpacking the samples or removing the packing
material.
a. The laboratory shall use the shipping container temperature indicator bottle
4.1.5 Sludge Sample Shipments reading as the sample temperature.
b. To determine the temperature, invert the bottle several times, remove the cap,
1. Use a 24-hour (overnight) delivery service for samples that are shipped to a laboratory. and insert a calibrated thermometer.
c. Allow a minimum of three (3) minutes, but not greater than five (5) minutes
2. To avoid shipping delays and compromising sample holding times, contact the shipping prior to taking the measurement. The thermometer used shall be calibrated and
company prior to sample collection. The shipping company can help determine the capable of measuring within an accuracy of ±1°C.
appropriate customs arrangements that must be made. d. If a temperature indicator bottle is not present in the shipping container, an
alternative means of determining shipping container temperature can be used.
3. Appendix B provides sample shipping forms that may help to avoid delays in customs. e. Under no circumstances shall a thermometer or any other device be inserted into
a sample bottle for the purpose of determining shipping container temperature.
4. Samples will be shipped in cool boxes with sufficient insulation and artificial refrigerant f. Other devices, such as an infrared thermometer, which can measure temperature
("blue ice"), or ice contained in double zip-lock bags, to maintain a sample temperature may be used if they are calibrated ±1°C.
of between 2°C and 8°C for the duration of transportation. Shipping containers that g. The desired sample temperature when it is received at the laboratory is 2°C to
leak fluid, such as melting ice water, will likely be returned to the shipper. 8°C.
i. If the sample temperature is greater than 4°C and less than 10°C, the
5. Containers should be held upright during shipment. Use bubble wrap around individual laboratory shall note the issue and provide an exception report with the
glass containers and use adequate packing material to prevent movement during sample test report.
shipment, cushion from shock, and reduce the risk of leakage. ii. If the sample temperature exceeds 10°C when received at the laboratory,
the laboratory shall contact the client and inform them of the temperature
6. The sampling team must maintain physical custody, or use custody seal tape on the deviation. The client may decide not to perform testing on these samples.
sample cool boxes.
3. If the laboratory encounters problems with samples or related documentation (e.g.
7. The sampler shall be responsible for all handling, processing, and custody of the mixed media, sample pH, sample documentation and paperwork such as Traffic Report/
samples, including taking samples to the nearest servicing airport, bus station, or other Chain-of-Custody), the laboratory shall immediately contact the sampler for a resolution.
carrier.
ZDHC Wastewater and Sludge Laboratory Sampling and Analysis Plan (SAP) ZDHC Wastewater and Sludge Laboratory Sampling and Analysis Plan (SAP)
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32 334.2.2 Sludge Sample Holding Time
Dyes – Azo (Forming -
1. In general, minimising the time between sample collection and analysis will provide Restricted Amines)
more reliable and representative analytical data. Extraction:
Dyes – Carcinogenic or - 7-days from collection
2. Figure 7 presents both the recommended and maximum holding times for each of the Equivalent Concern Analysis:
sludge testing parameters. Dyes – Disperse (Sensitising) - 40-days from extraction
Flame Retardants -
3. If a sample exceeds the maximum holding time the test results will be reported. Glycols -
However, any test results for samples that exceeded the maximum holding time must Halogenated Solvents 7 days 14 days
be flagged with the following data qualifier: “Maximum holding time exceeded. Red Organotin Compounds 24 hours 7 days
flag in the ZDHC Gateway – Wastewater Module. Probable error in results due to the Perfluorinated and
holding time” Polyfluorinated Chemicals -
(PFCs) Extraction:
Figure 7 – Sludge Sample Holding Time Otho-Phthalates – Including 7-days from collection
all ortho esters of Phthalic - Analysis:
Sludge Parameter Recommended Holding Maximum Holding Time Acid 40-days from extraction
Time Polycyclic Aromatic -
Anions Hydrocarbons (PAHs)
Cyanide 24 hours 14 days Volatile Organic Compounds 7 days 14 days
Metals (VOC)
Trace Metals 28 days 6 months ZDHC MMCF
Chromium-Hexavalent (VI) 24 hours 28 days Heavy metals 28 days 6 months
Mercury - 28 days Total Organic Carbon, TOC 7 days 14 days
ZDHC MRSL V1.1
Alkylphenol (AP) and Extractable Organic Halogen 7 days 14 days
Alkylphenol Ethoxylates - Extraction: Compounds, EOX
(APEOs): Including all 7-days from collection Adsorbable Organic
Isomers Analysis: Halogen Compounds, AOX, 7 day 14 days
Chlorobenzenes and - 40-days from extraction if requested
Chlorotoluenes
Chlorophenols -
ZDHC Wastewater and Sludge Laboratory Sampling and Analysis Plan (SAP) ZDHC Wastewater and Sludge Laboratory Sampling and Analysis Plan (SAP)
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34 354.2.3 ZDHC Sludge Parameters 4.2.5 Quality Systems
The sludge parameters are listed in the ZDHC Wastewater Guidelines. 1. The minimum quality assurance measures for organic chemical analysis of wastewater
and sludge are presented in Figure 4.
2. The quality assurance testing in Figure 8 is required for each of the ZDHC sludge
parameters. This data will be reported with the sample results and used by ZDHC to
4.2.4 Required Reporting Limits and Standard Test Methods for assess data quality and validate the analytical data
Sludge Figure 8: Minimum Quality Assurance Measures for Organic Chemical Analysis
Target Points to be checked
1. The ZDHC approved standard analytical/test methods and required reporting limits for Measure Description Frequency
value (examples)
each of the sludge parameters are presented in the ZDHC Wastewater Guidelines.
A. Routine
2. All test results will be reported on a dry-weight basis. Covering
Method sample 1 per Cleanliness of laboratory glassware and
3. The required reporting limits were established with consideration to achieving these blank preparation < MDL batch equipment
levels with good laboratory practices. and
measurement
4. The methods are based on requirements in the European Union, the United States of An inde-
America, India, and China. Alternate methods, such as those required by the regulatory Calibration pendently ± 20 1 per Check instrument condition/drift, clean
agency in the region in which the wet manufacturing occurs, may be used with prior Check sourced/ % batch and re-calibrate, stability standards
ZDHC review. prepared
standard
For GC
methods.
Substance Correction of injection
Internal with physico- 50 – Every error. Choice of
Standard chemical 150% sample Method specific: internal
properties surrogate as alternative standard or
similar to the surrogate or a
analyte combination
Substance Check sample thereof is
which has meth- preparation procedure method/
similar od Every and internal standard analyte
Surrogate physico- specif- sample correction. Method dependent
chemical ic specific: internal
properties to standard as alternative
the analyte
ZDHC Wastewater and Sludge Laboratory Sampling and Analysis Plan (SAP) ZDHC Wastewater and Sludge Laboratory Sampling and Analysis Plan (SAP)
Version 1.3 | January 2021 Version 1.3 | April 2021
36 37B. In case of problematic samples
(e.g. internal standard recovery too low, phase separation issues etc.) Note:
Duplicate Prob- • General suitability of the analytical approach is demonstrated via method validation.
Duplicate undergoing < 35 % lematic Flag results • Matrix to be encountered for wastewater and sludge analysis is less diverse/concentrated
complete RPD samples than for process chemicals (ZDHC MRSL).
process only • Therefore, initial method validation is deemed to sufficiently cover most sample types
Spike onto and a comparatively leaner QC program is applied.
Matrix sample Prob- • Specific, problematic sample matrices, which are not covered by the validation, require
Spike matrix Method lematic additional QC measures.
Matrix (duplicate) specific samples Flag results • In case of conflict, quality assurance measures specified by the applied standard, the
Spike undergoing only accreditation body, or local authority shall prevail.
Duplicate complete
process 2. The quality assurance testing in Figure 9 is required for each of the ZDHC sludge
C. For method validation parameters. This data will be reported with the sample results and used by ZDHC to
Multi-Point Min. 5-point r² ≥ Valida- assess data quality and validate the analytical data.
Calibration calibration 0.995 tion Linearity, working range
excl. origin Figure 9 – Required Quality Assurance Testing for Sludge
Extract the
standard Method
Field Method Calibration Lab ISTD and
Parameter
Recovery through the and Valida- Blank Blank Check* Duplicate Surrogate
(LCS) test analyte tion Recovery without influence of matrix
procedure specific Anions
without Cyanide - X X X -
matrix Metals
Repeatabil- Matrix spike Method Trace Metals - X X X X
ity replicates and Valida- Robustness, recovery with matrix Chromium-Hexavalent - X X X -
(matrix under analyte tion influence, UoM, general fitness for use (VI)
spike repli- repeatability specific Mercury X X X X -
cate) conditions ZDHC MRSL V1.1
Reference to ≤ WWG Alkylphenol (AP) and
ZDHC Waste- RL Alkylphenol Ethoxylates - X X X X
Limit of water Guide- Ideal: Valida- (APEOs): Including all
Detection lines; various ≤½ tion Sensitivity, LoD, LoQ Isomers
methodolo- WWG
gies can be RL
applied. * calibration check conducted with a second source standard
ZDHC Wastewater and Sludge Laboratory Sampling and Analysis Plan (SAP) ZDHC Wastewater and Sludge Laboratory Sampling and Analysis Plan (SAP)
Version 1.3 | April 2021 Version 1.3 | April 2021
38 394.2.6 Sludge Sample Storage
Chlorobenzenes and - X X X X
Chlorotoluenes 1. All samples will be stored under custody at between 2°C to 8°C (unless otherwise
Chlorophenols - X X X X specified by the analytical method).
Dyes – Azo (Forming - X X X X
Restricted Amines) 2. The samples may be disposed of 60 days after the final laboratory report is issued.
Dyes – Carcinogenic or - X X X X
Equivalent Concern
Dyes – Disperse - X X X X 4.3.0 Reporting and Deliverable Requirements
(Sensitising)
Flame Retardants - X X X X Reporting11 here means the submission of test data/results onto the ZDHC Gateway –
Glycols - X X X X Wastewater Module by ZDHC Accepted Laboratories on behalf of suppliers. It is vital that
Halogenated Solvents X X X X X the integrity of test data in the Gateway is at its highest possible standard. This will, among
other things, support the ZDHC Roadmap to Zero Programme in making scientific and data
Organotin Compounds - X X X X driven decisions necessary to shape the future of our industry.
Perfluorinated and 1. All test data must be reported using the ZDHC Gateway Electronic Data Reporting
Polyfluorinated X X X X X (EDR) System. The EDR guidelines and reporting template are publicly available on the
Chemicals (PFCs) ZDHC website.
Otho-Phthalates – I
ncluding all ortho esters - X X X X 2. The use of reporting formats other than those approved in the EDR will be deemed
of Phthalic Acid non-conformance. Such data is unacceptable and resubmission in the specified format
Polycyclic Aromatic - X X X X will be required.
Hydrocarbons (PAHs)
Volatile Organic X X X X X 3. All ZDHC Accepted Laboratories are expected to follow the data reporting requirements
Compounds (VOC) specified in the ZDHC Gateway Electronic Data Reporting (EDR) System Guidelines for
ZDHC MMCF wastewater and sludge, available on the ZDHC website.
Heavy metals Mercury x x x x
Total Organic Carbon, _ x x x _
TOC
Extractable Organic
Halogen Compounds, _ x x x _
EOX
Adsorbable Organic
Halogen Compounds, _ x x x _
AOX, if requested For more information please read the latest version of the ZDHC Wastewater Guidelines and the ZDHC Gateway User Terms
11
and Conditions document.
ZDHC Wastewater and Sludge Laboratory Sampling and Analysis Plan (SAP) ZDHC Wastewater and Sludge Laboratory Sampling and Analysis Plan (SAP)
Version 1.3 | April 2021 Version 1.3 | April 2021
40 414.4.0 Data Validation Appendix A
Example Chain of Custody Form
• ZDHC routinely requests laboratory QA/QC information from randomly selected ZDHC
Accepted Laboratories. The following information may be requested for data review:
a. Calibration Curves
b. Method Blank Instrument Reports
c. Instrument Calibration Check Sample Reports
d. Laboratory Control Sample Instrument Reports
e. Laboratory Duplicate Instrument Reports
f. Matrix Spike and Matrix Spike Duplicate Instrument Reports
g. Sample Custody Documentation
• The quality assurance and quality control results associated with the ZDHC sample will
be assessed by ZDHC to validate the analytical data. Quality assurance results that fail
to meet ZDHC guidelines may result in the rejection of sample results.
ZDHC Wastewater and Sludge Laboratory Sampling and Analysis Plan (SAP) ZDHC Wastewater and Sludge Laboratory Sampling and Analysis Plan (SAP)
Version 1.3 | April 2021 Version 1.3 | April 2021
42 43Appendix B
Shipping and Customs Forms 3. Toxic Substance Control Act (TSCA) Certification. This form certifies that a sample is not
a material which is hazardous to ship by air freight.
If the following forms are completed and accompany the samples during
international shipment, the chance for shipping delays in customs will be minimised:
1. Safety Data Sheet (SDS) for water samples. This illustrates that the wastewater
samples are not some type of known hazardous material. Search on Google to find
some publicly available examples.
2. Customs declaration forms for various countries, such as the one presented below,
can be found at this link: https://www.bing.com/images/search?q=Customs+Declara-
tion+Form+PDF&FORM=IDINTS
ZDHC Wastewater and Sludge Laboratory Sampling and Analysis Plan (SAP) ZDHC Wastewater and Sludge Laboratory Sampling and Analysis Plan (SAP)
Version 1.3 | April 2021 Version 1.3 | April 2021
44 45You can also read
